Abstract
Electrooxidation of renewable and CO(2)-neutral biomass for low-cost hydrogen production is a promising and green technology. Various biomass platform molecules (BPMs) oxidation assisted hydrogen production technologies have obtained noticeable progress. However, BPMs anodic oxidation is highly dependent on electrocatalysts, and the oxidation mechanism is ambiguous. Meanwhile, the complexity and insolubility of natural biomass severely constrain the efficient utilization of biomass resources. Here, we develop a self-sacrificing and self-supporting carbon anode (SSCA) using waste corncobs. The combined results from multiple characterizations reveal that the structure-property-activity relationship of SSCA in carbon oxidation reaction (COR). Theoretical calculations demonstrate that carbon atoms with a high spin density play a pivotal role in reducing the adsorption energy of the reactive oxygen intermediate (*OH) during the transition from OH(-) to *OH, thereby promoting COR. Additionally, the HER||COR system allows driving a current density of 400 [Formula: see text] at 1.24 V at 80 °C, with a hydrogen production electric consumption of 2.96 kWh Nm(-3) (H(2)). The strategy provides a ground-breaking perspective on the large-scale utilization of biomass and low-energy water electrolysis for hydrogen production.